JPS59197037A - Method for processing photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To release timely a photographically useful reagent by processing at weak alkalinity (9-12pH) by processing a photosensitive material contg. a specified precursor compound of the reagent in the presence of hydroxylamines. CONSTITUTION:A blocked photographic reagent which releases a photographically useful reagent by the cleavage of the 4--7-membered ring contg. a carbonyl group, e.g., a compound represented by the formula is used. A photosensitive silver halide material contg. said blocked photographic reagent in its constituent layer, preferably the silver halide emulsion layer is processed with a processing soln. contg. about 10<-3>-1mol/l hydroxylamines. In the formula, A is a photographically useful group bonded through a hetero atom; Q is -CO- or -SO2-; X is a bivalent timing group bonded to the imidomethyl group through an oxygen atom; R<1> is a substituent on the phenyl ring; m is 1-4; and n is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for processing silver halide photographic materials,
More specifically, it includes at least one carbonyl fund.
The present invention relates to a method for processing a silver halide photographic light-sensitive material containing a polymeric V cursor compound that releases a photographically useful reagent upon cleavage of a ring of 7 to 7 members.

Adding a photographically useful photographic reagent to a photographic light-sensitive material in advance to exhibit its effect has different characteristics from when it is used by incorporating it into a processing solution. Its features include, for example, that photographic reagents that are easily decomposed under acidic/alkali or oxidizing/reducing conditions and cannot withstand long-term storage in processing baths can be effectively used in the IF process; It may become easier to use the necessary photographic reagents at the necessary timing during processing, or it may be necessary only where necessary, i.e., in a certain layer of a multilayer photosensitive material and layers in its vicinity. It can be established that the amount of photographic reagents present can be varied as a function of silver halide development, etc. However, if a photographic reagent is added to a photographic light-sensitive material in an active form, it will decompose during storage before processing due to the influence of heat or oxygen that reacts with other components in the photographic light-sensitive material. Due to this, the expected performance cannot be achieved during processing. As a method for solving such problems, there is a method of blocking the f-occupant group of a photographic reagent and adding it to a photographic light-sensitive material in a substantially inactive form, that is, as a photographic reagent precursor. When useful photographic reagents are dyed, blocking functional groups that significantly affect the spectral absorption of the dye can be used to shift the spectral absorption toward shorter or longer wavelengths, resulting in a dye with a corresponding spectral range of sensitivity. ...It has the advantage that even if it coexists in the same layer as the silver halide emulsion layer, there is no reduction in sensitivity due to the so-called filter effect. If a useful photographic reagent is an antifoggant or a development inhibitor, blocking the active groups can suppress the desensitizing effect caused by adsorption to photosensitive silver/silver oxide and the formation of silver salts during storage. At the same time, by releasing these photographic reagents at the required timing, there are advantages such as reducing fog without impairing sensitivity, suppressing overdevelopment fog, and being able to stop development at the required time. . When useful photographic reagents are developing agents, auxiliary developers, or fogging agents, blocking the active groups or adsorbing groups can prevent various adverse photographic effects caused by the formation of semiquinones and oxidants due to air oxidation during storage, or There are advantages such as prevention of electron injection into silver halogenide, which prevents fog nucleation during storage, and as a result, stable processing can be realized. Even if the photographic reagent is a bleach accelerator or a bleach/fixing accelerator, by blocking the active groups, it is possible to suppress the reaction with other components contained therein during storage and remove the blocking groups during processing. By removing it, it has the advantage that the desired performance can be achieved at the required time.

As mentioned above, the use of precursors for photographic reagents can be an extremely effective means for fully demonstrating the performance of photographic reagents. However, on the other hand, these precursors must satisfy very strict requirements. It has to be something. In other words, it must be able to satisfy the contradictory requirements of being stable under storage conditions and releasing the photographic reagent promptly and efficiently by unblocking the blocking group at the required timing during processing. .

Several blocking techniques for photographic reagents are already known. For example, those using blocking groups such as acyl groups and sulfonyl groups described in the specifications of JP-B No. 447-≠≠, JP-B No. 61-Taro No. 22, ! ! -3119.27, which utilizes a blocking group that releases a photographic reagent through the so-called reverse Michael reaction, published by Tokuko Sho! ≠−327
．． No. 27, JP-A No. 57-/339≠φ, No. 77-/3
! ri4'j issue, same! A method utilizing a blocking group that releases a photographic reagent upon the production of quinone methide or a quinone methide-like compound through intramolecular electron transfer as described in the specification of JP-A-Shojjt-! Those utilizing the intramolecular confinement reaction described in the specification of No. 13330, or JP-A No. 7-7 Jj≠/, No. J7-/3!917,
same! 7-/7ri gψλ described in the specification! Techniques that utilize ring cleavage of six-membered or six-membered rings are known as well-known techniques. These known techniques are stable under storage conditions, but the release rate of photographic reagents during processing is too low, requiring high alkaline treatment with a pH of 2 or higher, or
Even if the release rate is sufficient with a treatment solution of H de~/2, it has the disadvantage that it gradually decomposes under storage conditions, impairing its function as a precursor. These drawbacks can be attributed to the reliance on attack by OH- ions to release photographically useful reagents from blocked photographic reagents. That is, the usual development of silver halide photographic materials is carried out with a developer having a pH of 2 to 12;
) and during treatment (pH ~7.2), the difference in OH- ion concentration is IO2~105. Thus, for example, a blocked photographic reagent that releases a photographically useful reagent with a half-life of 3 minutes (half of the amount added takes 3 minutes to decompose) upon treatment at pH 10 will, upon storage (as pH = J), 3 minutes x/(7-30
It is estimated that it decomposes with a half-life of 1,000 minutes and 10,000 SOO hours. This means that half of the amount used will decompose after approximately 3 weeks of storage, which is completely impractical. Similarly, in the treatment of pH / □A blocking compound that releases with a half-life of 3 minutes during treatment has a half-life of decomposition during storage of about 30 weeks, which is io times longer than that, which is a very unsatisfactory value. However, it can be said that it is difficult to put it into practical use in terms of storage stability.

On the other hand, in conventional color development processing, the sensitivity/fog ratio is lower when the antifoggant is applied in the middle of development than when it is added at the beginning. In addition to the dramatic improvements, the exceptional utility of anticapri precursors in color development processes is disclosed. Also, special application for 1977-20
34A≠t5 Same J-7-, 2/≠323, Same! 7-22
In 2g Hiro, in conventional color development,
It is disclosed that pyrazolidone precursor compounds significantly contribute to development acceleration and high sensitivity.

Therefore, the seventh object of the present invention is to overcome the greatest difficulties in utilizing precursor compounds for photographically useful reagents, which are stability under storage conditions and ensuring release of photographically useful reagents based on timing during processing. The object of the present invention is to provide a highly versatile general method that can satisfy the contradictory requirements described above. A second object of the present invention is to provide a method that can realize timely release of photographic reagents even in processing at a relatively low pH of 9 to 2. A third object of the invention is to provide sensitivity/power.

The object of the invention is to contain at least l carbonyl groups≠
Photosensitivity combined with blocked photographic reagents that release photographically useful reagents upon negative or 7-negative ring cleavage.
This was achieved by a method for processing a 710 Ge/Silver Cide photographic material, which is characterized in that a photographic material containing a Rogge/Silver Cide emulsion layer is processed in the presence of hydroxylamines.

Examples of blocked photographic reagents that release photographically useful reagents upon cleavage of a ≠ to 7-membered carbonyl group containing at least / carbonyl groups include, for example, compounds represented by the following general formulas (1) to (V). can be mentioned.

General formula (1) (1) General formula (n) 〇 General formula (111) General formula (VI (However, in general formula (t), A represents a photographically useful group bonded via a hetero atom. and Q is -CO- or -5
O2- is represented, X represents a divalent timing group bonded to the imidomethyl group via an oxygen atom, and Hl represents a substituent on the phenyl nucleus. It represents an integer of mB, o or l-≠, and n represents O or /.

In general formula (II), AXX and n have the same meanings as in general formula (1), and Z is -C1l, R,, -0-1-s-
1-NR9-, Y represents a nonmetallic atomic group necessary to form an o-member to 7 negative term, and l represents 0 or /.

RXFL and )L each represent a substituent.

In general formula (III), A, X, 几, m, n
has the same meaning as general formula (1), and R represents a substituent.

In general formula (IV), AXXXQ, R, and mn have the same meanings as in general formula (1), and RXR represents a substituent on the nitrogen atom.

In the general formula (V), A% X% RXrnz n has the same meaning as in the general formula (1), and RXR represents a substituent.

) In the general formulas CI) to (■), A is a known photographic reagent substituted with a hetero atom, specifically mercaptotetrazoles, mercaptothiadiazoles, benzotriazoles or i/dazoles. Typical anti-capri agents, pyrazolidones, hydroquinones or P
- Developing agents (auxiliary developers) represented by phenylene diamines, fogging agents or nucleating agents such as hydrazines, hydrazides, ≠ salts or acetylenes, haloke true reagents such as thioethers, hypo or rhodaninos It also contains a photographic reagent having a redox function that releases redox, such as a coloring material for a color diffusion transfer sensitive material or a DIR compound.

X in general formulas (I) to (V) represents a divalent timing group, which is bonded to the methyl group via an oxygen atom,
Represents a group that rapidly releases A after being cleaved as X-A during processing. As such a linking group, JP-A Sho-O ψ-
/≠5A by the intramolecular ring-opening reaction described in the specification of Yu 13j
Those that emit A by intramolecular electron transfer as described in British Patent No. 207.2363, JP-A-Sho, 3-7-/J-≠23φ, etc., JP-A-S7-” t
Linking groups such as those that release A with the elimination of carbon dioxide gas as described in Yurizahiro No. 2, etc., or those that release A with the elimination of formalin as described in Patent Application Sho Orr 203t≠B. can be mentioned. Regarding the representative X mentioned above,
Their structural formulas are shown below.

(A) (A) -0-C-(A) -0CH2-(A)1 The substituent R on the phenyl nucleus in general formulas CI), (II[), (IV) and (V) is fluorine , halogen yA atom such as chloro, brome, etc., alkyl group with carbon number /-, 2θ,
Aryl group with 6 to 2 carbon atoms, alkenyl group with carbon number λ to 2t, alkoxy group with carbon number /~/J, carbon number <-
26 aryloxy groups, C/~20 alkylsulfonyl groups, C6~. arylsulfonyl group with 2 O, a co- or tertiary amino group substituted with an alkyl group with ii/~20 carbon atoms, or an aryl group with carbon number A-2t, or an alkyl group with carbon number/-20 or carbon number, respectively t
-2t aryl group i! A ureido group, an aminosulfonamide group, a carbamoyl group, a sulfamoyl group, a carbonamide group, a sulfonamide group, a carbamate group, an oxycarbonyl group, an acyloxy group, a carbonate ester group, an acyl group, or a carboxy group, which may be substituted. , represents a sulfo group, a cyano group and a nitro group. The alkyl group, alkenyl group, and aryl group described above may be further substituted with the various substituents described above. m desirably represents 0 or/~2.

In the general formula (II), Z represents 10B7B8-10-1-s-5-NR9-, and forms a j-membered or 7-membered term together with L and Y, and l is. When , a ring is formed. R7
, R8, H, and 9 are each a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having a carbon number/-20, a carbon number 1-,
z represents an aryl group with 6 carbons, an alkoxy group with carbon ffi/ to /4, or an aryloxy group with carbon number t to λA, and may have a substituent. 2 is -CR7R8-1
-〇- is more preferable.

Y represents a nonmetallic atom group forming an o-membered or 7-membered ring together with Z, and the J-membered ring formed includes succinimide, maleimide, oxazolidinone, thiohydantoin,
Hydantoy 7, urazol, parabanic acid, etc. can be mentioned. Examples of the membered ring include glutaric imide, 3-oxyglutaric imide, barbylic acid, uracil, and benzoxazinedione. Preferred are succinimide, oxazolidinone, parabanic acid, glutarimide, and barbylic acid, and more preferably succinimide and oxazolidinone. The 7-membered ring is preferably dihydroazepi/-2,7-dione. When l is O, the ≠-membered ring is preferably a β-lactam.

R2 in the general formula CI) is a hydrogen atom, carbon number/~l
O represents an alkyl group or an aryl group having 6 to 2 carbon atoms, and the alkyl group and aryl group may have a substituent. R2 preferably represents a hydrogen atom or an aryl group having 6 to 10 carbon atoms.

In general formula (IV), R 1 is the number of carbon atoms/
Represents an alkyl group having ~16 carbon atoms, an aryl group having A-24 carbon atoms, an alicyclic group having j~10 carbon atoms, and a heterozygous residue having carbon atoms/~IO, each of which may have a substituent. .

R and R are more preferably an alkyl group with a carbon number of 1 to 1 and a carbon number of 1. , io represents an aryl group 3 and a substituted or unsubstituted pyridyl group.

R5 in the general formula (V) has the same meaning as 几 and R in the general formula (■), and is preferably an alkyl group having 1 to 1 carbon atoms, an aryl group having t to 10 carbon atoms, and a substituted or Represents an unsubstituted pyridyl group, and R6 is represented by the general formula (I[[
), and preferably represents a hydrogen atom or an aryl group.

The hydroxylamines used in the present invention have the general formula (V
l).

General formula (Vl) In general formula (M), RIOlR11 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterozygous residue; , 11 may be combined with each other to form a term, or H,1'O1B 11 may be further substituted with a hydroxylamino group to form a bis-form or a tris-form.

Y represents a hydrogen atom or a hydrolyzable group. The term "hydrolyzable group" as used herein refers to a group that generates a dihydroxylamino group upon hydrolysis during the current treatment, and is a blocking group for the hydroxylamino group.

B 10 and BJll are preferably hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, and z-2 carbon atoms, respectively.
The alkyl group and the aryl group may have other substituents, and R10 and Bll may form a j-& membered ring.

When the hydroxylamine represented by the general formula (Vl) is added to the treatment liquid and used, Y is a hydrogen atom,
In terms of solubility, BIOlBll has hydrogen atoms and carbon numbers, respectively! - It is preferable that B 10 , B 11 form an alkyl group and B 10 , B 11 capyrolidi/, piperidi/, morpho97, more preferably B 10 , B 11
11 is a hydrogen atom, a methyl group, an ethyl group, a λ-methoxyethyl group, and a tetrahydro-2-furfuryl group, respectively. On the other hand, in the general formula (Vl), when Y is a hydrogen atom and it is used by adding it to the sensitive material in advance, B10, The sum of the carbon numbers of B 11 is approximately IO
The above is preferable, and more preferable specific examples include B10 and B11 being phenyl, cyclohexyl, octyl, respectively, or R10 being methyl or ethyl, and B11 being decyl, dodecyl, tetradecyl, hexadecyl. , is an octadecyl group. When added to a light-sensitive material, it is more preferable to use a blocked compound, and in this case it is extremely useful since it is possible to impart diffusion resistance to the blocking group.

j1 Hydroxylamines represented by the formula (VI), for example, a photographically useful reagent with filling and cleavage of a group member to a seven-membered member containing at least / carbonyl groups represented by the general formulas (1) to (-V) The detailed reason for the effect of the present invention in significantly accelerating the release of photographically useful reagents from photographic reagents that have been coated and released is unknown at present and is a surprising fact. On the other hand, the specification of JP-A No. 1983/1983 describes the compounds represented by the general formulas CI) and (n), and the specification of JP-A No. 474 describes the compounds of the general formula (CI) and (n). 1■)
The release mechanism of a photographically useful reagent is shown for a precursor containing a compound represented by 'h' in the specification of 1983-33330. According to it, general formula (1) ~
Deblocking of the compound shown in (V) was performed using OHe io/
It is presumed that this is based on cleavage caused by nucleophilic attack on the carbonyl carbon, followed by electron transfer or intramolecular ring closure reaction.

If these hypotheses are correct, these general formulas CI) ~
Deblocking of the compound represented by (V) results in the general formula (Vl)
The effect of the present invention, which is significantly accelerated by the hydroxylamines shown in , is that the hydroxylamines make a nucleophilic attack on the carbonyl carbon instead of the OHe ion, thereby significantly promoting ring splitting. Wouldn't that be interpreted as such? However, it is not entirely clear why cleavage-type compounds exhibit such an accelerating effect more specifically, and it is thought that this phenomenon should be referred to as substrate specificity. Therefore, it must be said that it is extremely difficult to clarify the details.

Shown by general formulas (1) to (V)! All of the hydroxylamines represented by the general formula (Vl) of the recursor compound have a great effect of accelerating the release of useful photographic reagents, but among them, the saccharin derivatives whose Q in the general formula CI) is 18O□- , the phthalide derivatives represented by the general formula (III) and the general formula (V) show particularly remarkable release acceleration effects and have particularly favorable characteristics.

As can be easily seen from the above detailed description of the present invention, it is in principle extremely difficult for the present invention to achieve both stability during storage and timely release of photographically useful reagents during processing. It is particularly useful in conventional photographic materials that are processed at relatively low pHs of pH -12.

Here, with ordinary photographic materials, the development center (
silver halide emulsion grains with latent images or capri nuclei)
A sensitive material that forms multiple images by reduction with a developing agent that follows the Elz rule, and refers to materials other than diffusion transfer methods.

The amount of the blocked photographic reagent represented by the general formulas (I) to (V) of the present invention to be added varies depending on the photographically useful reagent to be released, but the mercapto-based anticapritic agent is per mole of silver/Q -10 mole. ＼Preferably 1o-6 to 10-2
The azole anti-capri agent represented by benzotriacyl is 10 to 10 moles per mole of silver, preferably /θ-5 to l0-2 mole. Auxiliary developers such as virazolidones have lo-4 to l/mole of silver.
0-E-nyl, preferably 10'' to j moles.

Developers such as hydroquino/s, aminephenols, and p-phenylenediamines have a 10-4
~10 moles, preferably i'o-2~! It is a mole. The fogging agent or nucleating agent represented by hydrazines, hydrazides, Q-class salts, acetylenes, etc. is 10 to 10-1 mol per 7 mol of silver, preferably lo-6 to 10
-2 moles. Silver halide solvents such as thioethers, hypo or rhodanines have a concentration of 10% per mole of silver.
The amount of the azo dye and the coloring material for color diffusion transfer sensitive materials is 10 to io mol, preferably lo-2 to 1 mol, per mol of silver.

When adding hydroxylamines represented by the general formula (Vl) to the processing solution, the amount added is lo-3 to lmog/β
, preferably 10" to jxIO" mol/l. or,
When added to a photosensitive material, 1 mol of silver F) 10
Mol to 1 mol, preferably 10 mol to 10
It is a mole.

Next, specific compounds of precursors represented by general formulas (I) to (V) and hydroxylamines represented by general formula (■) will be listed, but the present invention is not limited to these.

Compounds m, p, / described in JP-A Sho-Orr/369≠No.2
AA-111,,j'C(I)-(j)
0 0 (I)-1) 0 CI)-(7) 0 (1)-(f) OCI(3 m, p, /2j ~/2A 80m, p +
/4t2~/<4! 'C(1)-(ri)
0 (I)-(#)) 0 (I)-(//) '0 256- m, p , , / ♂l~/g3 °cm, p ,
200-20.2 °C (1)-(/-2)
0(I)-(/4') 0
m, p, /33 °C Compounds described in JP-A No. 7-/3, No. 9ψ, m, p, 2
/! N2/7 °c m, p, 207~. 2/J °Cm, p,
220~223 °CIn, p, /A/ ~/&
3 °C2H5 CH2CH2NH8O2CH3 % Kaisho J'7-/7 lamps 4t, No. 2 described compound CI)-(
-22) Co(I)-(-23) (1) Compound described in JP-A Shoj'7-/7gritλ No. JP-A Shoj
7-/3!9≠Compound (I)-(,!≠)
011 (II)-(1) 0 Tokukai Showa Orichi/
Compounds listed in JJ Tadata No. m, p, Zahiro~rj
'C (n) - (3) 0 (n) - (j)
0 JP-A-67-/3! Same as described in Rihiro No. 2 JP-A No. 7-/33 Described in Rihiro No. 2 m, p, //IN/2/ 0C JP-A No. 7-
711≠ Same as described in No. 1 0 (III)-i) Compound described in Patent Application No. 5♂-/G No. 30j Same as above (II[)-(♂) (III)-(ri) Cm)-(10) Special Same as the compound described in Gansho J'J'-/Ko3oJ'
Upper Cm), -C//) (I [[) - (/, 2) Qj (1) -
C/3) C.

02NH2 Compound described in Japanese Patent Application No. Sho II-//777 Same as above (II[)-(/4t) (III) -(/evening) (III)-(#) Patent Application Sho II-//777 ! -//Same as the compound described in No. 474 (l[I)-(/7) (II)-C/r) (nl)-(/ri) Same as the compound described in Patent Application Sho II-// &7J
CN)-C3) 0 (IV)-(g) (IV)-(-t) JP-A-Shoj! Compound described in No.-33330 Same as above (IV)-(B OH (IV)-(7) Compound described in Terakai No. 11-13330 Same as above (IV)-(,S') O (V)-(/) Special Compound described in Kaisho 3!-33330! Compound (V)-(,2) described in Kaisho jj-33330
(V JP-A-Sho!!-J3330 Compound) - (J) 1 JP-A-Sho! Compound (Vl)-(/
) NH2OH-Hα('ill)-(f)
(HOCH2CH2) 2N-0)I°“)-(/
/) He-1. □ OH3 (Vl)-(/-2) rtc4H9NHOH(M
l-(/3) nC3H□7NHOH(Vl)-(
-2-2) C"CO2H2,)2N-OH-1/2
Horse so.

(Vl)-(23) (■) (2+) nC,,H37NHOH-H
c7! H (Vl)-(-2♂) 0'H (Vl)-(JO) CVi)-C3/) (■)-(3,2) General compounds represented by general formulas CI) to (V) Synthesis methods and specific synthesis examples for some compounds are disclosed as follows.

Compounds of general formula (i) and general formula (II); JP-A-5
7-/33ri ≠ No. 9 specification, and S7 Dai 17ri gda No. 2 specification Compound of general formula (■): JP-A-7-74Jφ/ specification, Patent application Sho! Zaichi 1i6'io and the same jza-/≠3
0. Compounds of general formula (IV) and general formula (V): JP-A-Sho!
,! -33330 Specification The specific compounds shown in this patent can be synthesized according to the synthesis method described in the above patent specification, but compounds that are not specifically described in the above patent specification ,
Their melting points are shown.

Some of the hydroxylamides represented by the general formula (Vl) can be easily prepared manually as reagents, and can also be easily synthesized according to general synthesis methods described in the following literature. For example, oxidation of amines (B, C, Chal
lis and A,R.

'I'he Chemistry' by But Ier
of the Amino Group, 3 +20-
331 pages.

Interscience Publishers,
New York, / 6g year), reduction of oxy-A (H.

Feuer and B +F, Vinquent
, Journal of American Chem
ical 5ociety.

Cope reaction of amine oxide (A, C, Cope and E
,R.

Trumbull, Organic Reactio
ns.

//, 3/7-≠ri3. /30 years), addition reaction of hydroxylamine to olefins (M, S.

Gibson, The Chemistry o
f theAmino Group, t/-A
! Page, Interscience Publisher
s, New York, 19Alr), and the substitution reaction of activated norite with hydroxylamines (US Patent No. J, IA Ri, Isi), etc. are well known.

Also, US Patent No. 31g6φ, 131, US Patent No. 3°2g7
, No. 1211, 3, 21r7. lZj No. 3.2, No. 3,03ψ, No. 3,1103.03, No. 3. Specific compounds of the hydroxylamide class are described in the specification.

Specific synthesis examples of some of the newly synthesized compounds among the t-membered or 7-membered precursor compounds having a carbonyl group represented by general formulas (I) to (V) used in the present invention are shown below. show.

Synthesis Example 1 Synthesis of Exemplified Compound CI)-C1/)> Commercially available Nobi m = trophthalimide (,tg, 1ILQ), reduced iron r3oy), ammonium chloride (/, 3f) were mixed with isopropyl alcohol (≠"ynl), water (≠0w1
) and acetic acid (4' ml), and the mixture was heated and stirred on a steam bath for 1 hour. The solid substance was filtered while hot, and the solid substance was washed with acetone (300@l×3 times) while hot. The F solution was collected and the solvent was distilled off using a rotary evaporator to obtain crude crystals, which were then recrystallized from methanol/acetone to obtain /7
0.2f of the title compound was obtained. Synthesis of m,p,2j00C<do≠-aminophthalimide (,it,iy>) and pyridine (,r, 2ml) were combined with dimethylacetamide (100
, l) and add ice water to approx. While maintaining the temperature at 0C, p-toluenesulfonyl chloride (/y) was added dropwise over about 10 minutes.

After the dropwise addition was completed, stirring was continued for about 30 minutes at room temperature, and then stirring was continued for another hour at room temperature, and the reaction solution was poured into ice water (toOml).
The precipitated crystals were counted. The title compound 299 was obtained by recrystallization from methanol. m, p6.
2jO6C< ≠-(p-toluenesulfonamide)phthalimide (z
, r, 7f) and 3! Thiformin aqueous solution (70ml
) in water (70I+It) and dioxa/(-21Om
l) into the mixed solution and heat it on an oil bath at about 100"C for 7 hours.
heated for an hour. The title compounds 2≠, 3 were obtained by cooling the reaction solution to room temperature, pouring it into ice water, and counting the precipitated crystals.
I got 1/. m, p.

1900C decomposition N-hydroxymethyl-Hiro-(p-toluenesulfonamide) phthalimide (/7.39) and phosphorus tribromide (
/ j dat) f: Pe/ze/(,z o o ml) and heated for about g00C,, 1 hour. The reaction solution was cooled, and the precipitated crystals were collected from F and recrystallized from methanol/ethyl acetate to obtain the title compound/39.

Synthesis of m,p,/fol/zaza00 CI)-(//)
0πt), ! -mercapto=/-tetrahydrophtha of sodium salt of phenyltetrazole (6g)/
The solution (lootrtl) was gradually added dropwise at room temperature. After reacting at room temperature for 2 hours, the reaction solution was poured into ice water, and the resulting crystals were separated to obtain a crude product. By recrystallizing from a mixed solvent of ethyl acetate/methanol, N-(/-phenyl-tertetrazolylthiomethyl)-ψ-(p-)/sulfonamido)phthalimide/j, 41. I got g. m, p, 202-20tA 0C Synthesis Example 2 Synthesis of Exemplary Compounds CI)-C/3) and (I)-(/≠)> /-phenylene/L/-3-pyrazolidinone +7g and triethylamine! ,/g to dimethylacetamide 1IO
ql and stirred at room temperature under a nitrogen atmosphere. A solution of 20 filtrate of dimethylacetamide was added dropwise over 30 minutes. After stirring for a further 3 hours, the drained water was extracted with processed chloroform/00.1. ri o o form layer 10
After washing twice with 011 water, the mixture was concentrated with sodium sulfate. Using a chromatography column filled with silica gel, the compound produced with a developing solvent of ethyl acetate-chloroform is separated, and by recrystallization from toluene, the desired compound /-phenyl-,2-(N-phthalimidomethyl)- 3-pyrazolidinone CI)-(/J) 7
．． /9(m,p,176~lzaII)0C),/-7
j-=ru-3-(N-phthalimidomethyloxy)-2
-Pyrazoline (I)-(c, t, tg(m, p.

1-207°C) were obtained, respectively. (I)-(13
) and CI)-(HA0) isomers were determined from the IR spectra, 'HNMR and 13CNMR spectra.

Synthesis Example 3 <Synthesis of exemplified compound CI)-(/ff)> Saccharif (/139) and 31% formalin solution (io
Add o7> to water (-200~l) and place on oil bath for 1oo
Heated at 0C for 70 hours. The precipitated crystals were counted and the title compound '+tJ/I! I got f.

m, p, i2r ~/, 220C N-hydroxymethylsaccharin (70f) and phosphorus tribromide (32,71) were added to Hanze/(2! Stirred. The reaction solution was cooled, water (2jOπt) was added to precipitate crystals, and the crystals were washed with water to obtain the title compound 7f. Synthesis of m, p, / tl 2~l≠4tOc (1)-(/♂) N-bromomethylsaccharin (/3.19), l-phenyl-3-pyrazolidinone (//, tada) and triethylamine (j ,!;l) to tetrahydrone (20θπ
After stirring at room temperature in a nitrogen stream for 2 hours, the reaction mixture was added to water (, lo o mt ) and diluted with ethyl acetate (1
00, lx 2 times). After drying the extract with magnifying glass,
A crude product was obtained by distillation. Recrystallization from ethyl acetate gave 16 g of N-(nophenyl-3-pyrazolidino/-2-ylmethyl)saccharin (CI)-(/za)). m, p, 20 - 2/3 °C Synthesis Example 4 Synthesis of Exemplified Compound (n)-(-2)> Glutaric acid imide (,27y), 31% formalin solution (,z
o txl ) was added to water (≠0 ml) and heated at 1000C on an oil bath for 1 hour. Water was completely distilled off using a rotary evaporator to obtain a crude product of N-methylolglutaric acid imide. Without purification, this was added to 200 psi benzene and phosphorus tribromide (7,jm
1) and heated under reflux for 1 hour. Water was added, the benzene layer was separated, and the crude product obtained by distilling off the benzene was recrystallized from ethyl acetate/n-hexane to obtain the title compound of about λzy. m, p, / otr'C(n)
Synthesis of -(-2) Dissolve N-bromomethylglutarimide (//, jg) in tetrahydrofuran (CJOytrl) and add the sodium salt of l-phenyl-yo-mercaptotetrazole (1/,!19) to this solution at room temperature. ) of tetrahydrofuran (
The solution was added dropwise. After stirring at room temperature for about 7 hours, precipitated NaQ! was removed and tetrahydrofuran was distilled off to obtain a crude product, ethyl acetate/n-hexano recrystallization L, N-(/-phenyl-7-tetrazolylthiomethyl)glutaric acid imide lg. Ta.

m, p, zahiro ~ zr 0c Precursors represented by general formulas CI) to (V) used in the present invention may be used in combination of 1.2 or more.

The blocked photographic reagents (precursors) represented by general formulas CI) to (V) of the present invention can be used in silver halide emulsion layers, colorant layers, undercoat layers, protective layers, etc. of silver halide photographic light-sensitive materials.
It may be added to any layer including an intermediate layer, a filter layer, an antihalation layer, an image receiving layer, a cover sheet layer, and other auxiliary layers. A silver halide emulsion layer is preferable.

In order to add the precursor used in the present invention to these layers, the precursor may be added to the coating solution for forming the layer in its original state, or it may be added to a solvent such as water, alcohol, etc. that does not have an adverse effect on the photographic material. It can be dissolved and added to an appropriate concentration. Alternatively, the precursor can be dissolved in a high boiling point organic solvent and/or a low boiling point organic solvent, and added by emulsifying and dispersing the solution in an aqueous solution. In addition, polymer latex may be impregnated by the method described in Chikai Sho 3 No. 321j'3, same Ta/-j Tata ≠ No. 1, same-32 Yo 12, U.S. Pat. , may be added.

The precursor may be added at any time during the manufacturing process, but it is generally preferable to add the precursor immediately before coating.

It is more preferable that the hydroxylamine represented by the general formula (Vl) is added to a processing solution such as a developer and reacted with the precursor represented by the general formulas (1) to ('l) during development. It is also possible to add at least one type of hydroxylamine of about 10 or more to the sensitive material in advance and to react with the precursor by diffusion in the film during processing.In this case, the hydroxylamine and the Precursors are preferably added to different layers to prevent contact with each other during coating and during storage prior to processing. Hydroxylamines can be added to basically any layer, but halogenated Color material layer, undercoat p excluding silver emulsion layer
It is preferable to add it to a layer, a protective layer, an intermediate layer, a filter layer, an antihalation layer, an image-receiving layer, a cover sheet layer, and other auxiliary layers.

When hydroxylamines are added to a processing solution, it is preferable to use them as a component of a developing bath. In other cases, the effect of the present invention can be exerted by adding it to a pre-bath or processing bath following the development processing bath.

The present invention can be used, for example, in a coupler-type color photographic material.

A common method for forming color images from color photographic materials is to convert silver halide materials into primary aromatic materials in the presence of a can-coupler that has the ability to react with the oxidized form of a developing agent to form a dye. This is a method of obtaining azomethine or indium dye by developing with amine/developing agent. This color development method is basically 13/year, D.

It was invented by Mannesgr, [, Godowski], and various improvements have been made since then.
It is used in the industry worldwide today.

In this system, a subtractive color method is usually used for color reproduction, with a silver halide emulsion selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image forming agents, which are complementary colors, respectively. is used. To form a yellow image, for example, an acylacetanilide or dibenzoylmethane coupler is used, and to form a magenta image, a pyrazolone, pyrazolobenzimidazole, cyanoacetophenone or indazolo/type coupler is mainly used. Phenolic couplers, such as phenols and 7-tols, are primarily used to form cyan images.

Conventionally known methods of adding or dispersing couplers to emulsions and methods of adding them to gelatin/silver halide emulsions or hydrophilic colloids are applicable.

For example, a method of mixing and dispersing a coupler with a high boiling point organic solvent such as dibutyl phthalate, tricresyl phosphate, wax, higher fatty acid and its ester, etc., for example, US Pat. No. 2,3017. Ri3ri No. 2.322.0.
The method described in No. 27, etc. A method of mixing and dispersing a coupler with a low boiling point organic solvent or a water-soluble organic solvent. A method of dispersing couplers in combination with a high boiling point organic solvent.

For example, US Patent No. 2. Zaoi, Ilo issue, No. 2゜za0
/, No. 171, No. 2. The method described in Rihiro 7.3 Otsu θ issue etc.

Couplers used in combination with the precursor and hydroxylamines of the present invention include, for example, the following known couplers.

A specific example of a magenta coloring coupler is U.S. Patent No. 2゜1.0
0.71, 2,713, t (#, 3.07
．． ．． No. 2,113, No. 3, 1.27, 2/, No. 3, No. 3
．． 3//, No. 4176, 3. ≠/ri, 3ri No. 1, same 3. Evening/Ri, 4L, No. 27, Same 3. Evening r, 3/ri issue,
Same 3. j♂2,3λλ, same 3. t/r.

jot issue, 3.1341.701, 3, g? /
, No. 1llr, West German Patent/, g10. <tli issue, West German patent application (OLS), z, pθg, &4 issue, same, 2
．． 44/7, ri≠j issue, same 2. ≠/Za, Rijri No., same co, 4t2≠, ≠t7 No., special public Shogo ot.

No. 31, JP-A-2012 No. 7.2-r? 7
No. 22, same Kota 12ri 53g, same≠turf≠027
Issue, same to-izri 33, same! 2-G 2/2/ issue,
Same ≠ Turf 1702g, same jθ-tO, 133, same Ta 1-26 Ta ≠ No. 1, same Ta 3-! ! /22, etc.

Specific examples of yellow coloring couplers are given in U.S. Patent No. 22g7j, 0
Jt No. 7, 3, 27. j, No. 304, same 3゜Hirooza,
/9≠No.3. ! Oh/,/! J issue, same J,! 12.
No. 322, same j, 72! F, No. 07.2, 3.1
9/, 'i'4 bow, West German patent/,! +7゜za 2/issue,
West German Application Publication No. 2, 21, No. 17, 2. ．． 21/,
3t/No., same λ, 4t/≠, θO6, British Patent 1. φ
2! , No. 020, Tokko Shota/-10713, Tokko Sho F7-2t/33, No. 48 knee 731≠7, No. kl
-10, Z otsu 3 otsu no., 10-13 pi no. 1, same jO-/
ko33≠λ, 30-/301fi112, z
i-co/No. 127, tO-47tjO, S2-
It is described in g2 Ko 24, 32-//okori issue, etc.

Specific examples of shear/couplers are given in US Pat. No. 2,31.

Octopus No. 2, Same 2. v3pi, No. 272, same, v7Ifi
, No. 293, 2, j2/, ri07, 2゜19
! ;, Za, No. 27, 3,03≠, Zatako, 3.3
1/, ≠ No. 76, same 3. Hirojza, No. 373, same 3. ≠7
&,! No. 63, 3, 1113. ri No. 71, same j, 1
9/, 31'3, 3,71,7. '1/1, Dohiro, 00+, Ri2ri, West German patent application (Ol, S)-
2. Mineda, g30, same, 2. tAj Hiroshi.

No. 32, Tokukai Sho p, -5yt Jr., same j/-,2
No. 60344, same φg-yo No. 031, same! /-/≠tza, 2g issue, same j2-A9tλφ issue, same! This is the one described in λ-taOri No. 3.

As a colored coupler, for example, U.S. Patent No. 3.117
/,, No. 160, No. 2.12/', No. 901, No. 3,
0Jti, No. 192, Tokko Sho p4! -2oi6, same3
No. 1-22331, No. 1-22331, No. 1-22331, No. 1-22331, No. 1-22331, No.
2da No. 61, specification of JP-A No. 31-2603φ, same j2
-≠2121 specification, West German patent application C0L8)2. t
Those described in Allr, YZ9 can be used.

As DIR Cub 2-, for example, US Patent 3゜2.2
7. Jj Hiro issue, 3, 1. /7, 2ri No. 1, 3.70
/, 7Il) No. 3, 3.7ta 0.31≠ No., 3. Otsu 32,311! r, West German patent application (OLD) λ, ≠l
≠, oot issue, same 2. ≠! Hiroshi, No. 307, 2. II O≠, No. 32, British Patent 233. Hiroyo≠ issue, JP-A-32
-#9A2≠No., same≠Tar12U333, special public show 5i
-tt, those described in iφ can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development; for example, as described in US Pat. φIII No. 3, 37! λ
No., West German Patent Application (OLD) λ, Hiroshi/7. Rida,
Those described in JP-A-3.2-1!27/ and JP-A-3-1-1 can be used.

When applying the present invention to color diffusion transfer photography, peel-off (peel anomite) type or
3! A, 4AJ'-33t 7, JP-A-Shota 0-/
Integrated type as described in No. 30'IO and British Patent No. 330, j, Z'1, no peeling required as described in JP-A-37-//3ψj It is possible to take the configuration of a molded film unit.

The use of a polymeric acid layer protected by a neutralizing timing layer in any of the above types of formats
This is advantageous in widening the allowable range of processing temperatures.

The present invention can also be used in black-and-white photographic materials. Examples of the black-and-white photosensitive materials include X-ray film for direct exposure, black-and-white film for general photography, lithographic film, and scanner film.

Other constitutions of the silver halide photographic material of the present invention, such as a method for producing a silver halide emulsion, halogen composition, crystal habit, grain size, chemical sensitizer, antifoggant, stabilizer, surfactant, gelatin There are no particular restrictions on curing agents, hydrophilic colloid binders, matting agents, dyes, sensitizing dyes, anti-fading agents, anti-color mixing agents, polymer latex, brighteners, antistatic agents, etc. For example, Re5earchD
Volume 7 of isclosure/7 p22-p31 (
You can refer to the description in 1997 (1972).

Further, there are no particular limitations on the exposure method, development method, etc. of the silver halide photographic material of the present invention, and for example, the above (Re
search Disclosure) 2nd g~3
Any of the known methods and known treatment liquids as described on page 0 can be applied. This photographic processing may be either a photographic processing that forms a silver image (black and white photographic processing), or a photographic processing that forms a dye image (color photographic processing), depending on the purpose. Processing temperature is normal
The temperature is selected between r 0C and jo 0C, but the temperature may be lower than lr 0c or higher than jo 0c.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-
Pyrazolidones (e.g. l-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p
-aminophenol), etc. can be used alone or in combination. The developer generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc.
Furthermore, it may contain a solubilizing agent, a color toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, etc., if necessary.

The photographic emulsion of the present invention can be subjected to a so-called "lith type" development process.

When forming a dye image, conventional methods can be applied.

For example, negative-positive method (e.g. “Journal of
the 5ociety of Motion P
ictureand Te1vision Eng
ineers”, A/vol. (1953), &&
7-70/pages); developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least seven uniform exposures or other suitable capri processing; A color reversal method that produces dye positive image scratches by performing color development; a silver dye bleaching method in which a photographic emulsion layer containing a dye is exposed and developed to form a silver image, and this is used as a bleaching catalyst to bleach the dye. used.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., guamino-N, N-diethylaniline, 3-methyl-ψ-amino-N, N-diethylaniline, guamino-N-ethyl-N- β-hydroxyethylaniline, 3-methyl-q-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethyl-N-
β-methanesulfamide ethylaniline, t-amino-
3-methyl-N-ethyl-N-β-methoxyethylanili/etc.) can be used.

In addition, Photograph by F. A. Mason
icProcessing Chemistry (
Published by FocalPress, 226-2.
Page 29, US Patent Co., /? 3,0/J- issue, same co, j7
Those described in No. 2° EAII, JP-A-4-1-933, etc. may be used.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As bleaching agents, compounds of polyvalent metals such as iron CI[I], cobalt (IV), chromium (Vl), and copper (n), peracids, quinones, and nitroso compounds are used. The present invention will be further explained below with reference to Examples.

Example 1 3.2 x 10' moles of sample were dissolved in 'Ivtl acetonitrile and this was mixed with acetonitrile/1. It was added to a mixture of yxl and 20 ml of Britton-Robison buffer solution and reacted at 1.2j 0C. After a certain period of time (the pH was adjusted with a buffer solution), acetic acid was added to lower the pH to 6°J and stop the reaction. The released antifoggant was quantified using high performance liquid chromatography, the quadratic reaction rate constant was determined, and the half-life t//2 was calculated. Next, hydroxylamine 3. x 10-4 mol is acetonitrile/A>
The half-life t' was obtained by the same procedure except that it was added to
//, 2. The accelerating effect of hydroxylamine was calculated by comparing with no additive, and the accelerating effect of hydroxylamine was determined using a known precursor that releases an antifoggant without ring cleavage (comparative example (A-/
) and Comparative Example (A--2)). (Table-/
) (A-/) (A-2) As is clear from Table 7, the precursors represented by general formulas CI) to (V) have a pH of 1 by adding hydroxylamine.
0,0 and pi (//.

In O, the release acceleration effect was 2.3 to 37 times greater.

On the other hand, the reverse Michael-type release precursors shown in Comparative Example A-/ and Comparative Example-2, which were not caused by ring cleavage, were either slowed down by the addition of hydroxylamine or had almost no effect.

Therefore, the effect of accelerating the release of sinkers by hydroxylamine is due to the cleavage of j-negative or t-membered molecules containing at least / carbonyl groups as shown in the general formulas (I) to (V) shown in the present invention. This is particularly noticeable in precursors that release photographically useful reagents.

Example 2 Measurement of the release acceleration effect of hydroxylamine on pyrazolidone precursor The release acceleration effect of hydroxylamine on pyrazolidones was determined by the same method as shown in Example 1, and the results are shown in Table-
Shown in 2.

As shown in Table C, it can be seen that hydroxylamine has a remarkable release acceleration effect even in precursors that release pyrazolidones upon ring cleavage.

Example 3 On a cellulose triacetate film support provided with an undercoat layer, the antifoggant precursor and magenta coupler (C-/) shown in Table 3 were dissolved in tricresyl phosphate and ethyl acetate, An emulsion layer as shown below, which has been emulsified and dispersed in an aqueous gelatin solution, is applied, and the sample/~l!
It was created.

Application and amount of each substance is g/m2 or mol/m
It is shown in parentheses as 2.

(1) Emulsion layer negative silver iodobromide emulsion (grain size 1.jμ, silver/, A
×/θ-”mo1/m2) Magenta coupler 〇-/ (1,33×lθ-3mol/m2) Tricresyl phosphate (o, RiJ' (1/m2) Gelatin (z, jp/m2) (2) Protective layer 2, +L-dichloro-6-hydroxy-s-triazine sodium salt (o, or17m2) gelatin
(y, 3oy/m2) These films were left for 1 hour under the condition of 70% relative humidity at 0°C, then exposed to white light for sensitometry, and then subjected to the next color development process (A processing) was carried out. The density of the processed sample was measured under green light to obtain photographic data.

Color development process Time Temperature 1 Color 4108 3', is〃3x oC2 bleaching
White 6'30" 〃3 Wash 2' 〃4 Fix ≠
′〃5 Washing with water ≠′
〃6 Stability〃Here, the composition of each processing solution in the color development processing step is as follows.

Color developer water 10
0+-(N-ethyl-N-hydroxyethyl)amino-2-methylaniline sulfate! f Sodium sulfite! 1 potassium carbonate
30//potassium bicarbonate
7.2g potassium bromide
/0.2 (sodium monochloride
00.2p trisodium nitrilotriacetate /,
Add 2g water /1 (pH
10,/) bleach solution water za00
Ferric ammonium salt of ethylenediaminetetraacetic acid resistant 10oy disodium ethylenediaminetetraacetic acid 109 potassium bromide 1roy acetic acid
Add 10f water
/1 (pHA, 0) Fixer water za00
g1 ammonium thiosulfate /! O'j Sodium sulfite 10f Sodium hydrogen sulfite 2,! f Add water
/1(pIl; ,o) Stable liquid water s'o
o book t formalin (37chi) i
ytrl dry well 3
Add water to π, then add A to /l
In the processing color developer / l, hydroxylamine sulfate (Vl ) -C2) / 2 f! , bis(methoxyethyl)hydroxylami7CVI)-C3)lfl
and methylhydroxylamine hydrochloride (VI)-(3
)t'! The same process as A process was performed except that . These processes are referred to as B process, C process, and D process, respectively.

Table 3 shows the maximum color density values obtained by each treatment of sample/~/evening.

From Table 3, in samples λ to g, which are comparative examples, there is no clear difference in color density between the treatment liquid gA, which does not contain hydroxylamines, and the treatment liquid B-D, which contains hydroxylamines. On the other hand, in samples j-/j of the present invention, a large decrease in color density was observed with the BD treatment containing hydroxylamines, indicating that the hydroxylamines promoted the release of the antifoggant. That is clear.

The comparative compounds and couplers used here are as follows.

B-/C- Example 4 Coating samples/A to 2r containing an antifoggant and an antifoggant precursor were prepared in the same manner as in Example 3. These films were exposed in the same manner as in Example 3, and
A treatment was carried out in which p, og of hydroxylamine sulfate was added per liter of color developer (E treatment). The photographic properties obtained are shown in Table D.

From Table 3, it can be seen that there is no change in the photographic properties of any of the samples in treatment A, which does not contain hydroxylamine, but in treatment E, which contains hydroxylamine, the sample name/R It is clear that at 2 g, fog is reduced with almost no decrease in relative sensitivity.

A preferred embodiment of the present invention is as follows: t A processing method as claimed in the claims, characterized in that the blocked photographic reagent is represented by the following general formulas (I) to (V).

General formula CI) 〇 General formula (II) General formula (I represents a photographically useful group, and Q is -co- or -8
O2- is represented, X represents a divalent timing group bonded to the imidomethyl group via an oxygen atom, and R1 represents a substituent on the phenyl nucleus. m represents O or an integer of /~g, and n represents O or l.

In the general formula (n), A, X, and n have the same meanings as in the general formula CI), and Z is
B, 9-, Y represents a nonmetallic atomic group necessary to form a ta- to 7-membered ring, and l represents 0 or l. R7
, 'fL8 and R9 each represent a substituent.

In the general formula (II[), A, X, R,'', m.

n has the same meaning as in general formula CI), and R2 represents a substituent.

In general formula (IV), A% Xs 9% R1, m
, n have the same meanings as in general formula (1), and Kaede R3 and R4 represent substituents on the nitrogen atom.

In general formula (V), A, X, R,', m.

n has the same meaning as in general formula (I), and Kaede R5 and R6 represent substituents. ) The blocked photographic reagent has the following general formula (I, (I
II) or (V).

General formula (I') 〇 General formula (III) (R1) m.

General formula (V) However, the definitions of AX, R1, R2, R5, R6, m and n are the same as in the above embodiment 1.

3. The processing method according to the claims, characterized in that the processing is carried out with a developer having a pH of 12 to 12.

≠ A processing method according to claims, characterized in that the processing is carried out with a developer containing hydroxylamines and having a pH of ≠1λ.

! A treatment method according to the claims, characterized in that the hydroxylamine is a compound represented by the general formula (Vl).

Procedural amendment 1, case display Showa! Special Application No. 71♂♂3
No. 2, Name of the invention Processing method for silver halide photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4, Amendment Subject All entries in column 5 of the "Detailed Description of the Invention" in the MfU document and "Detailed Description of the Invention" in the list of contents of the amendment are amended as follows.

l) Second! "m, p, 200~202°cJ f"m, p on page αj-(1)
, 202~2θ Hiro'C4.

2) No. 27 page r (I) - 10 (I) O and correct it.

3) On page 31 and correct it.

3g page r(1)-(161 ” r (II [) - ([6) ” and correct it.

j) On page 32 r (III) −Qη ” r (m) - (17) ” and correct it.

t) Page r3 and correct it.

Claims (1)

[Claims] A photographic light-sensitive material comprising a light-sensitive silver halide emulsion layer in which a blocked photographic reagent is combined which releases a photographically useful reagent upon cleavage of a 7-membered ring containing at least a carbonyl group of hydroxylamine 1. A method for processing silver halide photographic materials, which comprises processing in the presence of .